WO2003093387A1

WO2003093387A1 - Heat-curable epoxy resin composition

Info

Publication number: WO2003093387A1
Application number: PCT/EP2003/003962
Authority: WO
Inventors: Andreas Kramer
Original assignee: Sika Schweiz Ag
Priority date: 2002-05-03
Filing date: 2003-04-16
Publication date: 2003-11-13
Also published as: US20050159511A1; EP1504073A1; AU2003229684A1; EP1359202A1; US20080073029A1; JP2010043288A; JP2005524736A; JP4515251B2; US7786214B2

Abstract

The invention relates to compositions containing: at least one epoxy resin A with on average more than one epoxy group per molecule; at least one epoxy adduct B with on average more than one epoxy group per molecule; at least one thixotropic agent C, based on a urea derivative in a non-diffusing support material; and at least one curing agent D for epoxy resins, which is activated by an increased temperature. According to preferred embodiments, the invention also relates to compositions containing at least one core-shell polymer E and/or filler F and/or reactive diluent G. The invention also relates to the use of said compositions as a single-component adhesive and to a method for producing the compositions. The invention further relates to the use of the thixotropic agent C, based on a urea derivative in a non-diffusing support material as an agent for increasing the impact resistance.

Description

SIKA SCHWEIZ AG Tüffenwies 16-22 CH-8064 Zurich (Switzerland)

HEAT-CURABLE EPOXY RESIN COMPOSITION

Technical field

The invention relates to heat-curing compositions which are distinguished by a simultaneous high impact strength and high glass transition temperature and can be used in particular as one-component adhesives.

State of the art

In the manufacture of vehicles and add-on parts as well as machines and devices, high-quality adhesives are increasingly being used instead of or in combination with conventional joining processes such as riveting and punching or welding. This creates advantages and new possibilities in production, for example the production of composite and hybrid materials or greater freedom in the design of components. For use in vehicle manufacture, the adhesives must have good adhesions on all substrates used, in particular electrolytically galvanized, hot-dip galvanized and subsequently phosphated steel sheets, oiled steel sheets and on various types of aluminum. These good adhesive properties must be maintained without major quality losses, especially after aging (changing climate, salt spray bath, etc.). If the adhesives are used as structural adhesives, the wash-out resistance of these adhesives is of great importance so that process safety can be guaranteed at the manufacturer.

The washout resistance can be achieved with or without pre-gelling. To achieve sufficient resistance to washing out the adhesive should be pasty and pre-gelled in a shell oven within a short time or by means of induction heating of the parts to be joined.

The adhesives for the body-in-white must harden under the usual curing conditions of ideally 30 minutes at 180 ° C. Furthermore, they must also be stable up to around 220 ° C. Further requirements for such a hardened adhesive or the gluing are the guarantee of operational safety both at high temperatures down to around 85 ° C and at low temperatures down to around -40 ° C. Since these adhesives are structural adhesives and therefore these adhesives bond structural parts, high strength of the adhesive is of the utmost importance.

Conventional epoxy adhesives are characterized by high mechanical strength, in particular high tensile strength and high tensile shear strength. When the bond is suddenly stressed, however, classic epoxy adhesives are usually too brittle and can therefore by no means meet the requirements of the automotive industry in crash conditions in which both large tensile and peel stresses occur. The strength at high, but especially at low, temperatures is also insufficient. Various approaches are proposed to reduce the brittleness of the epoxy adhesives in the event of sudden stress. Essentially, two methods are proposed in the literature for improving the impact strength of epoxy adhesives. On the one hand, the goal can be achieved by admixing at least partially crosslinked high-molecular compounds such as latices of core / shell polymers or other flexibilizing polymers and copolymers. On the other hand, by introducing soft segments, e.g. a certain increase in toughness can be achieved by appropriate modification of the epoxy components.

According to the first-mentioned technique, US Pat. No. 5,290,857 and US Pat. No. 5,686,509 describe how epoxy resins can be made more impact-resistant by adding a fine, powdery core / shell polymer into the epoxy resin. matrix is mixed. This creates highly elastic domains in the hard, brittle Epoxidmat ix, which increase the impact resistance. Such core / shell polymers are described in US 5,290,857 based on acrylate or methacrylate polymers. No. 5,686,509 describes similar compositions based on ionically crosslinked polymer particles, the core polymer of which consists of crosslinked diene monomers and the shell copolymer of crosslinked acrylic, methacrylic and unsaturated carboxylic acid monomers.

According to the second technique mentioned in patent

No. 4,952,645 describes epoxy resin compositions which have been made more flexible by reaction with aliphatic, cycloaliphatic or aromatic carboxylic acids, in particular di- or trimeric fatty acids, and with aliphatic or cyclo-aliphatic diols. Such compositions should be characterized by increased flexibility, especially at low temperatures.

The modification of epoxy adhesives using polyurethane-epoxy adducts is also known. The terminal isocyanate groups of prepolymers are reacted with at least one epoxy resin, giving a hot melt adhesive that is solid at room temperature. This method is described in EP 0343676.

It is also known that epoxy resins can be made more flexible with elastomers such as synthetic rubbers and their derivatives. The main effect is based on the partial miscibility of the epoxy resins and the corresponding derivatized synthetic rubbers, which results in heterodisperse phases in the manufacturing process, which have a comparable effect to the core / shell polymers. The setting of this superstructure depends both on the quantitative composition and on the process control during the hardening process. The literature known to the person skilled in the art describes carboxyl-terminated poly-butadiene-acrylonitrile copolymers which are reacted with epoxy resins as particularly preferred starting compounds for this flexibilization technique. In No. 5,278,257 and WO 0 037 554 describe epoxy adhesive formulations which contain adducts with epoxy end groups as main components, produced by the reaction of carboxyl-terminated butadiene-acrylonitrile or butadiene-methacrylate compounds (or also their styrene copolymers) with epoxy resins, and also phenolic contain terminated polyurethanes or polyureas. Such adhesives can have high values for peeling, impact or impact peeling stress.

In general, a major disadvantage of the prior art is that the glass transition temperature and / or the strength of the adhesives is reduced by increasing the impact strength, or that the strength is generally increased by increasing the glass transition temperature, but the impact strength and the adhesion and in particular the peel strength is reduced. This limits the use as structural structural adhesive very strongly, especially because extremely high demands are placed on a crash-resistant adhesive.

Furthermore, the use of liquid rubbers is very disadvantageous in that the extent of the phase separation and thus also the improvement in the impact resistance are very strongly influenced by the manufacturing or curing conditions, which leads to large fluctuations in the properties.

Presentation of the invention

It is the object of the present invention to provide new, one-component heat-curing compositions which are stable at room temperature, in particular adhesives and hot-melt adhesives, which on the one hand have high strength and on the other hand have a high glass transition temperature, advantageously one of at least about 85 ° C. This is achieved in particular without the use of liquid rubbers and the associated dependencies on the manufacturing or curing conditions. These properties are particularly important in order to guarantee bonding even in the event of an accident (crash) and thus to meet the most modern safety requirements in vehicle construction.

Surprisingly, this goal could be achieved by the composition according to the invention. In particular, it has been shown, unexpectedly, that an extremely strong improvement in impact strength can be achieved in particular by using a thixotropic agent based on urea derivatives in a non-diffusing carrier material, as described in patent application EP 1 152 019 A1. It was also unexpected that the epoxy adduct used in claim 1, which was optimized with regard to the glass transition temperature, did not bring about the expected reduction in impact strength.

The present invention relates to compositions which comprise at least one epoxy resin A with an average of more than one epoxy group per molecule; at least one epoxy adduct B with an average of more than one epoxy group per molecule; at least one thixotropic agent C, based on urea derivative in a non-diffusing carrier material; and contain at least one hardener D for epoxy resins, which is activated by elevated temperature.

According to preferred embodiments, compositions are also described which additionally contain at least one core / shell polymer E and / or at least one filler F and / or at least one reactive diluent G.

In addition, the use of this composition as a one-component adhesive and methods of producing the composition are described.

Furthermore, the use of the thixotropic agent C based on urea derivative in a non-diffusing carrier material is described as an agent for increasing the impact strength. Way of carrying out the invention

The present invention relates to compositions which contain at least one epoxy resin A with an average of more than one epoxy group per. Molecule; at least one epoxy adduct B with an average of more than one epoxy group per molecule; contain at least one thixotropic agent C based on urea derivative in a non-diffusing carrier material and at least one hardener D for epoxy resins which is activated by elevated temperature.

Epoxy resin A has on average more than one epoxy group per molecule. 2, 3 or 4 epoxy groups per molecule are preferred.

Epoxy resin A is preferably a liquid resin, in particular diglycidyl ether of bisphenol-A (DGEBA), of bisphenol-F and of bisphenol-A / F (the designation 'A / F' here refers to a

Mixture of acetone with formaldehyde, which is used as a starting material in its production). Due to the manufacturing process of these resins, it is clear that in the liquid resins also higher molecular weight

Components are included. Such liquid resins are, for example, as

Araldite GY 250, Araldite PY 304, Araldit GY 282 (Vantico) or D.E.R 331

(Dow) available.

The epoxy adduct B is an epoxy adduct of type B1 and optionally B2.

The epoxy adduct B1 can be obtained by the reaction of at least one dicarboxylic acid, preferably at least one dimeric fatty acid, in particular at least one dimeric C4-C20 fatty acid (corresponding to a C8-C40 dicarboxylic acid) with at least one diglycidyl ether, in particular bisphenol A diglycidyl ether, bisphenol F-diglycidyl ether or bisphenol A / F-diglycidyl ether. The epoxy adduct B1 has a flexibilizing character.

The epoxy adduct B2 can be obtained by the reaction of at least one bis (aminophenyl) sulfone isomer or at least one aromatic alcohol with at least one diglycidyl ether. The aromatic Alcohol is preferably selected from the group of 2,2-bis (4-hydroxyphenyl) propane (= bisphenol-A), bis (4-hydroxyphenyl) methane (= bisphenol-F), bis (4-hydroxyphenyl) sulfone, Hydroquinone, resorcinol, pyrocatechol, naphtho hydroquinone, naphthoresorcinol, dihydroxynaphthalene, dihydroxyanthraquinone, dihydroxy-biphenyl, 3,3-bis (p-hydroxyρhenyl) phthalide, 5,5-bis (4-hydroxyphenyl) hexahydro-4,7- methanoindane and all isomers of the aforementioned compounds. The preferred bis (aminophenyl) sulfone isomers are bis (4-aminophenyl) sulfone and bis (3-aminophenyl) sulfone. The diglycidyl ether is especially bisphenol A diglycidyl ether, bisphenol F diglycidyl ether or bisphenol A / F diglycidyl ether. Bis (4-hydroxyphenyl) sulfone is suitable as a particularly preferred aromatic alcohol. The epoxy adduct B2 has a rather rigid structure.

In a particularly preferred embodiment, the epoxy adduct B is a combination of epoxy adduct B1 and epoxy adduct B2.

The epoxy adduct B preferably has a molecular weight of 700 to 6000 g / mol, preferably 900 to 4000 g / mol, in particular 1000 to 3300 g / mol. “Molecular weight” or “molecular weight” is understood here and below to mean the molecular weight M _w . The epoxy adduct B is prepared in a manner known to those skilled in the art.

The total proportion of epoxy resin A is advantageously 12-50% by weight, preferably 17-45% by weight, based on the total weight of A + B. Here and in the following, the overall total is understood to mean the sum of all components belonging to this category. If, for example, a composition contains 2 epoxy resins A, the total proportion is the sum of these two epoxy resins.

The total proportion of epoxy resin A and epoxy adduct B is further advantageously 20-70% by weight, preferably 35-65% by weight, based on the weight of the total composition. A catalyst known to the person skilled in the art, such as triphenylphosphine, can be used for the synthesis of the epoxy adduct.

The composition also contains at least one

Thixotropic agent C, based on urea derivative in a non-diffusing carrier material. This thixotropic agent C advantageously contains a blocked polyurethane prepolymer as the carrier material. The production of such urea derivatives and carrier materials are described in detail in patent application EP 1 152019 A1.

The urea derivative is a reaction product of an aromatic monomeric diisocyanate with an aliphatic amine compound. It is also entirely possible to implement several different monomeric diisocyanates with one or more aliphatic amine compounds or one monomeric diisocyanate with several aliphatic amine compounds. The reaction product of 4,4'-diphenylmethylene diisocyanate (MDI) with butylamine has proven to be particularly advantageous.

The total proportion of the thixotropic agent C is advantageously 5-40% by weight, preferably 10-25% by weight, based on the weight of the overall composition. The proportion of the urea derivative is advantageously 5-50% by weight, preferably 15-30% by weight, based on the weight of the thixotropic agent C.

The composition according to the invention further contains at least one hardener D for epoxy resins, which is activated by elevated temperature. This is preferably a hardener which is selected from the group of dicyandiamide, guanamines, guanidines, aminoguanidines and their derivatives. Furthermore, catalytically active substituted ureas such as phenyl-dimethyl urea, in particular p-chlorophenyl-N, N-dimethyl urea (monuron), 3-phenyl-1, 1-dimethyl urea (fenuron) or 3,4-dichlorophenyl-N, N- dimethyl urea (diuron). Compounds of the class of imidazoles and amine complexes can also be used. Dicyandiamide is particularly preferred. The total proportion of hardener D is advantageously 1-6% by weight, preferably 2-4% by weight, based on the weight of the entire composition.

In a further embodiment, the invention contains

Composition further at least one core / shell polymer E. Preferably, the core of the core / shell polymer consists of a polymer with a glass transition temperature of -30 ° C or lower and the shell of the core / shell polymer consists of a polymer with a glass transition temperature of 70 ° C or higher. Examples of polymers that can be used as the core material are polybutadiene, polyacrylic acid and polymethacrylic acid esters and their copolymers or terpolymers with polystyrene, polyacrylonitrile or polysulfide. The core material preferably contains polybutadiene or polybutyl acrylate. Examples of shell polymers are polystyrene, polyacrylonitrile, polyacrylate and methaerylate mono, co or terpolymers or styrene / acrylonitrile / glycidyl methacrylate terpolymers. Polymethyl methacrylate is preferably used as the polymer for the shells. The size of such core / shell polymers is expediently 0.05-30 μm, preferably 0.05-15 μm. In particular, core / shell polymers with a size of less than 3 μm are used. Core / shell polymers are preferably used which contain a core of polybutadiene or polybutadiene / polystyrene. This core material is preferably partially cross-linked. Other core materials are polyacrylates and methacrylates, in particular polyacrylic acid and polymethacrylic acid esters and their copolymers or terpolymers.

The shell preferably consists of polymers based on methyl methacrylate, cyclohexyl methacrylate, butyl acrylate, styrene, methacrylonitrile.

Commercially available core / shell polymer products include F-351 (Zeon Chemicals), Paraloid and Acryloid (Röhm and Haas), Blendex (GE Specialty Chemicals) and the like. The total proportion of the core / shell polymer E is advantageously 3-20% by weight, preferably 5-12% by weight, based on the weight of the entire composition.

In a preferred embodiment, the composition additionally contains at least one filler F. These are preferably mica, talc, kaolin, wollastonite, feldspar, chlorite, bentonite, montmorillonite, calcium carbonate (precipitated or ground), dolomite, quartz, silicas (pyrogenic or precipitated), cristobalite, calcium oxide, aluminum hydroxide, magnesium oxide, hollow ceramic spheres, hollow glass spheres, hollow organic spheres, glass spheres, color pigments. The filler F means both the organically coated and the uncoated commercially available forms known to the person skilled in the art.

The total proportion of the total filler F is advantageously 5-30% by weight, preferably 10-25% by weight, based on the weight of the entire composition.

In a further preferred embodiment, the composition additionally contains at least one reactive diluent G carrying epoxy groups. These reactive diluents G are in particular:

Glycidyl ethers of monofunctional saturated or unsaturated, branched or unbranched, cyclic or open-chain C4-C30 alcohols, e.g. Butanol glycidyl ether, hexanol glycidyl ether, 2-ethylhexanol glycidyl ether, allyl glycidyl ether, tetrahydrofurfuryl and furfuryl glycidyl ether etc.

- Glycidyl ethers of difunctional saturated or unsaturated, branched or unbranched, cyclic or open-chain C2 - C30 alcohols, e.g. ethylene glycol, butane diol, hexane diol, octane diol digyl cidyl ether, cyclohexane dimethanol diolyl cidyl ether, neopentyl glycol diglycidyl ether etc.

- Glycidyl ethers of trifunctional or polyfunctional, saturated or unsaturated, branched or unbranched, cyclic or open-chain Alcohols such as epoxidized castor oil, epoxidized trimethylolpropane, epoxidized pentaerythrol or polyglycidyl ether of aliphatic polyols such as sorbitoi etc.

- Glycidyl ethers of phenol and aniline compounds such as phenyl glycidyl ether, cresol glycidyl ether, p-tert-butylphenyl glycidyl ether, nonylphenol glycidyl ether, 3-n-pentadecenyl glycidyl ether (from cashew nutshell oil), N, N-diglycidyl ether

- Epoxidized tertiary amines such as N, N-diglycidylcyclohexylamine etc.

- Epoxidized mono- or dicarboxylic acids such as neodecanoic acid glycidyl ester, methacrylic acid glycidyl ester, benzoic acid glycidyl ester, phthalic acid, tetra- and hexahydrophthalic acid diglycidyl ester, diglycidyiester of dimeric fatty acids etc.

- Epoxidized di- or trifunctional, low to high molecular weight polyether polyols such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether etc.

Hexanediol diglycidyl ethers are particularly preferred,

Polypropylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether.

The total proportion of the reactive diluent G carrying epoxy groups is advantageously 1-7% by weight, preferably 2-6% by weight, based on the weight of the total composition.

The use of the composition as one-component adhesives has proven particularly successful. In particular, heat-curing one-component adhesives can be realized with this, which are characterized both by high impact strength and by a high glass transition temperature. Such adhesives are required for the bonding of heat-stable materials. Heat-stable materials are understood to mean materials which at least have a curing temperature of 120-220 ° C., preferably 150-200 ° C. are dimensionally stable during the curing time. In particular, these are metals and plastics such as ABS, polyamide, polyphenylene ether, composite materials such as SMC, unsaturated polyester GRP, epoxy or acrylate composite materials. The application in which at least one material is a metal is preferred. A particularly preferred use is the bonding of the same or different metals, in particular in the body-in-white in the automotive industry. The preferred metals are above all steel, in particular electrolytically galvanized, hot-dip galvanized, oiled steel and subsequently phosphated steel, and aluminum, in particular in the variants typically occurring in automobile construction.

Above all, the desired combination of high crash resistance and high operating temperature can be achieved with an adhesive based on a composition according to the invention. Such an adhesive is contacted with the materials to be bonded and is typically cured at a temperature of 120-220 ° C, preferably 150-200 ° C.

Of course, in addition to heat-curing adhesives, sealing compounds or coatings can also be implemented. Furthermore, the compositions according to the invention are not only suitable for automobile construction but also for other fields of application. Related applications are particularly obvious in the construction of means of transport such as ships, trucks, buses or rail vehicles or in the construction of consumer goods such as washing machines.

Hot melt adhesives can also be produced in a special way on the basis of the composition according to the invention. The hydroxyl groups formed in the epoxy adduct are reacted with isocyanate groups or isocyanate prepolymer. This increases the viscosity and requires hot application. Examples

The following shows some examples which further illustrate the invention but are not intended to limit the scope of the invention in any way. The raw materials used in the examples are as follows:

General production for production of the epoxy adduct B and its mixture with A (= A / B premix):

A / B premixing VM1 At 110 ° C under vacuum and stirring 123.9 g of a dimeric

Fatty acid, 1.1 g triphenylphosphine and 57.3 g adipic acid with 658 g of a liquid DGEBA epoxy resin with an epoxy content of 5.45 eq / kg reacted for 5 hours until a constant epoxy concentration of 2.85 eq / kg was reached. After the reaction had ended, an additional 118.2 g of liquid DGEBA epoxy resin were added to the reaction mixture. Other mixtures VM2 to VM4 were also produced. The adipic acid was replaced by various aromatic alcohols in such a way that a theoretically identical epoxy content of the binder of 2.80 - 2.95 eq / kg was achieved:

A / B premix α VM2

At 110 ° C., 123.9 g of a dimeric fatty acid, 1.1 g of triphenylphosphine and 95.0 g of 2,2-bis (4-hydroxyphenyl) propane (= bisphenol-A) with 658 g of a liquid DGEBA epoxy resin with an epoxy content of 5.45 eq / kg reacted for 5 hours until a constant epoxy concentration of 2.95 eq / kg was reached. After the reaction had ended, an additional 118.2 g of liquid DGEBA epoxy resin were added to the reaction mixture.

A / B pre-mix α VM3

At 110 ° C, 123.9 g of a dimeric fatty acid and 28.3 g of adipic acid, 1.1 g of triphenylphosphine and 47.3 g of bis (4-hydroxyphenyl) sulfone with 658 g of a liquid DGEBA epoxy resin with an epoxy content of 5.45 eq / kg were 5 hours under vacuum and stirring long implemented until a constant epoxy concentration of 2.85 eq / kg was reached. After the reaction had ended, an additional 118.2 g of liquid DGEBA epoxy resin were added to the reaction mixture.

A / B premix VM4 At 110 ° C under vacuum and stirring 123.9 g of a dimeric

Fatty acid, 1.1 g triphenylphosphine and 71.3 g bis (4-hydroxyphenyl) sulfone reacted with 658 g of a liquid DGEBA epoxy resin with an epoxy content of 5.45 eq / kg for 5 hours until a constant epoxy concentration of 2.82 eq / kg was reached. After the reaction had ended, an additional 118.2 g of liquid DGEBA epoxy resin were added to the reaction mixture. Thixotropic agent C The thixotropic agent C was produced according to patent application EP 1 152 019 A1 in a blocked prepolymer with the above-mentioned raw materials:

Backing material: Blocked polyurethane prepolymer: 5 600.0 g of a polyethene polyol (2000 g / ol; OH number 57 mg / g KOH) became the isocyanate in the presence of 0.08 g of dibbutyl-tin dilaurate under vacuum and stirring at 90 ° C. with 140.0 g of IPDI -terminated prepolymer until the isocyanate content remained constant. The free isocyanate groups were then blocked with caprolactam (2% excess). o Urea derivative (HSD1) in blocked polyurethane prepolymer:

68.7 g of MDI flakes were melted into 181.3 g of the blocked prepolymer described above under nitrogen and gentle warming. 40.1 g of N-butylamine dissolved in 219.9 g of the blocked 5 prepolymer described above were then added dropwise under nitrogen and with rapid stirring. After the addition of the amine solution had ended, the white paste was stirred for a further 30 minutes. After cooling, a white, soft paste was obtained which had a free isocyanate content of <0.1% (urea derivative content approx. 21%).

At most, further carrier material can be added to this mixture. For example, a further 4 g of carrier material (= block. Prepolymer) was added for the examples.

Adhesive formulations

Various adhesive compositions according to Table 1 were produced. After application at 50 ° C., the adhesives were cured in an oven at 180 ° C. for 30 minutes. All tests were carried out only after the adhesive had cooled to room temperature.

Test methods: Glass over temperature Tα (PIN EN ISO 6721-2 / PIN EN 61006)

The test specimens with the dimensions 50 x 10 mm were made from a 2 mm thick adhesive plate between 30 Teflon foils at 180 ° C for 30 minutes was hardened, punched out. Measurement: oscillation 1 Hz, temperature range - 50 - + 150 ° C, heating rate 2 K / min. The glass transition temperature Tg was set at the maximum of the curve of the mechanical loss factor (tangent δ).

Sugar resistance ZSF (PIN EN 1465)

The test specimens were made with electrolytically galvanized steel (eloZn) with the dimensions 100 x 25 x 0.8mm, the adhesive area was 25 x 10mm with a layer thickness of 0.3mm. Curing was carried out at 180 ° C. for 30 minutes. The train speed was 10mm / min.

Imoact Peel (ISO 11343)

The test specimens were made with electrolytically galvanized steel (eloZn) with the dimensions 90 x 25 x 0.8mm, the adhesive area was 25 x 30mm with a layer thickness of 0.3mm. Curing was carried out at 180 ° C. for 30 minutes. The impact speed was 2 m / s.

results

The results of the adhesive formulations in Table 1 show that the combination of high impact strength, high glass transition temperature and high strength can be achieved with the compositions according to the invention. Examples 1 and 7 not according to the invention show, compared to Examples 2 and 6, particularly clearly the positive influence of the thixotropic agent, or the urea derivative, on the impact resistance. Examples 2 to 6 show the influence of the epoxy adduct used and that at the same time an increase in impact strength and an increase in Tg can be achieved by the invention, while the tensile shear strength remains unchanged. Examples 9 and 10, in comparison with Examples 2 and 6, show that the desired properties can be achieved regardless of whether the composition is filled or unfilled. Examples 8 and 6 show that the presence of a core / shell polymer has a positive, albeit smaller influence on the impact resistance compared to the thixotropic agent or the urea derivative.

Claims

claims

1. Comprehensive composition

at least one epoxy resin A with an average of more than one epoxy group per molecule;

at least one epoxy adduct B, each with an average of more than one epoxy group per molecule;

at least one thixotropic agent C, based on urea derivative in a non-diffusing carrier material;

at least one hardener D for epoxy resins, which is activated by elevated temperature.

2. Composition according to claim 1, characterized in that the epoxy resin A is a liquid resin, in particular a bisphenol A diglycidyl ether, bisphenol F diglycidyl ether or bisphenol A / F diglycidyl ether.

3. Composition according to claim 1 or 2, characterized in that the epoxy adduct B

an epoxy adduct B1, which consists of at least one

Dicarboxylic acid and at least one diglycidyl ether is available; and optionally combined with an epoxide adduct B2, which is obtainable from at least one bis (aminophenyl) sulfone isomer or at least one aromatic alcohol and at least one diglycidyl ether; is.

4. Composition according to claim 3, characterized in that for the preparation of the epoxy adduct B1 as a dicarboxylic acid a dimeric fatty acid, in particular at least one dimeric C4-C20 fatty acid, and as diglycidyl ether bisphenol A diglycidyl ether, bisphenol F diglycidyl ether or bisphenol -A / F diglycidyl ether is used.

5. Composition according to one of claims 3 or 4, characterized in that for the production of the epoxy adduct B2 an aromatic alcohol selected from the group 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone, hydroquinone, resorcinol, pyrocatechol, naphthohydroquinone, naphthoresorcinol, dihydroxynaphthalene, dihydroxyanthraquinone, dihydroxy-biphenyl, 3,3-bis (p-hydroxyphenyl) phthalide, 5,5-bis (4- hydroxyphenyl) hexahydro-4,7-methanoindane and all isomers of the aforementioned compounds or and as diglycidyl ether bisphenol A diglycidyl ether, bisphenol F diglycidyl ether or bisphenol A / F diglycidyl ether is used.

6. Composition according to one of the preceding claims, characterized in that the epoxy adduct B has a molecular weight of 700 - 6000 g / mol, preferably 900 - 4000 g / mol, in particular 1000 - 3300 g / mol.

7. Composition according to one of the preceding claims, characterized in that the carrier material of the thixotropic agent C is a blocked polyurethane prepolymer.

8. Composition according to claim 7, characterized in that the urea derivative in the thixotropic agent C is the product of the reaction of an aromatic monomeric diisocyanate, in particular 4,4'-diphenylmethylene diisocyanate, with an aliphatic amine compound, in particular butylamine.

9. Composition according to one of the preceding claims, characterized in that the hardener D, a latent hardener from the group of dicyandiamide, guanamines, guanidines, and aminoguanidines.

10. Composition according to one of the preceding claims, characterized in that the total proportion of epoxy resin A and epoxy adduct B in total is 20-70% by weight, preferably 35-65% by weight, based on the weight of the entire composition ,

11. Composition according to one of the preceding claims, characterized in that the total proportion of epoxy resin A is 12-50% by weight, preferably 17-45% by weight, based on the total weight of A + B.

12. Composition according to one of the preceding claims, characterized in that the total proportion of the thixotropic agent C is 5-40% by weight, preferably 10-25% by weight, based on the weight of the total composition.

13. The composition according to claim 12, characterized in that the proportion of the urea derivative is 5-50% by weight, preferably 15-30% by weight, based on the weight of the thixotropic agent C.

14. Composition according to one of the preceding claims, characterized in that the total proportion of hardener D is 1-6% by weight, preferably 2-4% by weight, based on the weight of the total composition.

15. Composition according to one of the preceding claims, characterized in that at least one core / shell polymer E is additionally present.

16. The composition according to claim 15, characterized in that the total proportion of the core / shell polymer E is 3-20% by weight, preferably 5-12% by weight, based on the weight of the total composition.

17. Composition according to one of the preceding claims, characterized in that the core of the core / shell polymer E consists of a polymer with a glass transition temperature of -30 ° C or lower and the shell of the core / shell polymer E consists of a polymer a glass transition temperature of 70 ° C or higher.

18. Composition according to one of the preceding claims, characterized in that at least one filler F is additionally present.

19. The composition according to claim 18, characterized in that the total proportion of the filler F is 5 to 30% by weight, preferably 10 to 25% by weight, based on the weight of the entire composition.

20. Composition according to one of the preceding claims, characterized in that at least one reactive diluent G carrying epoxide groups is additionally present.

21. Composition according to one of the preceding claims, characterized in that the heat-cured composition has a glass transition temperature of at least 85 ° C.

22. A process for the preparation of a composition according to any one of claims 1-21, characterized in that at least one adducting step is carried out with a diglycidyl ether in the preparation.

23. Use of a composition according to any one of claims 1-21 as a one-component adhesive.

24. Use according to claim 23, characterized in that the adhesive is used for the bonding of heat-stable materials, in particular metals.

25. Use according to claim 23 or 24, characterized in that the adhesive is used as a structural adhesive in automobile construction.

26. Use of the thixotropic agent C based on urea derivative in a non-diffusing carrier material as an agent for increasing the impact resistance.

27. Use of the thixotropic agent C according to claim 26, characterized in that the carrier material C is a blocked polyurethane prepolymer.

28. Use of the thixotropic agent C according to claim 26 or 27, characterized in that the urea derivative is the product of

Reaction of an aromatic monomeric diisocyanate, in particular 4,4'-diphenylmethylene diisocyanate, with an aliphatic

Amine compound, especially butylamine.

29. Use of the thixotropic agent C according to one of claims 26-28, characterized in that the proportion of the urea derivative is 5-50% by weight, preferably 15-30% by weight, based on the weight of the thixotropic agent C.

30. A method for gluing heat-stable materials, in particular metals, characterized in that these materials are contacted with a composition according to one of claims 1 to 21 and a step of curing at a temperature of 120-220 ° C, preferably 150-200 ° C includes.